Cargando…
Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability
[Image: see text] Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium....
Autores principales: | , , , , , , , , , , , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8569803/ https://www.ncbi.nlm.nih.gov/pubmed/34677973 http://dx.doi.org/10.1021/jacs.1c07874 |
_version_ | 1784594716208136192 |
---|---|
author | Han, Guopeng Vasylenko, Andrij Neale, Alex R. Duff, Benjamin B. Chen, Ruiyong Dyer, Matthew S. Dang, Yun Daniels, Luke M. Zanella, Marco Robertson, Craig M. Kershaw Cook, Laurence J. Hansen, Anna-Lena Knapp, Michael Hardwick, Laurence J. Blanc, Frédéric Claridge, John B. Rosseinsky, Matthew J. |
author_facet | Han, Guopeng Vasylenko, Andrij Neale, Alex R. Duff, Benjamin B. Chen, Ruiyong Dyer, Matthew S. Dang, Yun Daniels, Luke M. Zanella, Marco Robertson, Craig M. Kershaw Cook, Laurence J. Hansen, Anna-Lena Knapp, Michael Hardwick, Laurence J. Blanc, Frédéric Claridge, John B. Rosseinsky, Matthew J. |
author_sort | Han, Guopeng |
collection | PubMed |
description | [Image: see text] Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li(3)P(5)O(14) and Li(4)P(6)O(17) based on extended layers and chains of phosphate, respectively. Li(3)P(5)O(14) presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li(6)O(16)(26–) chains. Li(4)P(6)O(17) features a new type of loop-branched chain defined by six PO(4)(3–) tetrahedra. The ionic conductivities and electrochemical properties of Li(3)P(5)O(14) were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li(3)P(5)O(14) enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10(–7) S cm(–1) at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li–P–O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li(3)P(5)O(14), which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries. |
format | Online Article Text |
id | pubmed-8569803 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-85698032021-11-08 Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability Han, Guopeng Vasylenko, Andrij Neale, Alex R. Duff, Benjamin B. Chen, Ruiyong Dyer, Matthew S. Dang, Yun Daniels, Luke M. Zanella, Marco Robertson, Craig M. Kershaw Cook, Laurence J. Hansen, Anna-Lena Knapp, Michael Hardwick, Laurence J. Blanc, Frédéric Claridge, John B. Rosseinsky, Matthew J. J Am Chem Soc [Image: see text] Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li(3)P(5)O(14) and Li(4)P(6)O(17) based on extended layers and chains of phosphate, respectively. Li(3)P(5)O(14) presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li(6)O(16)(26–) chains. Li(4)P(6)O(17) features a new type of loop-branched chain defined by six PO(4)(3–) tetrahedra. The ionic conductivities and electrochemical properties of Li(3)P(5)O(14) were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li(3)P(5)O(14) enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10(–7) S cm(–1) at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li–P–O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li(3)P(5)O(14), which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries. American Chemical Society 2021-10-22 2021-11-03 /pmc/articles/PMC8569803/ /pubmed/34677973 http://dx.doi.org/10.1021/jacs.1c07874 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Han, Guopeng Vasylenko, Andrij Neale, Alex R. Duff, Benjamin B. Chen, Ruiyong Dyer, Matthew S. Dang, Yun Daniels, Luke M. Zanella, Marco Robertson, Craig M. Kershaw Cook, Laurence J. Hansen, Anna-Lena Knapp, Michael Hardwick, Laurence J. Blanc, Frédéric Claridge, John B. Rosseinsky, Matthew J. Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability |
title | Extended
Condensed Ultraphosphate Frameworks with
Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical
Stability |
title_full | Extended
Condensed Ultraphosphate Frameworks with
Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical
Stability |
title_fullStr | Extended
Condensed Ultraphosphate Frameworks with
Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical
Stability |
title_full_unstemmed | Extended
Condensed Ultraphosphate Frameworks with
Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical
Stability |
title_short | Extended
Condensed Ultraphosphate Frameworks with
Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical
Stability |
title_sort | extended
condensed ultraphosphate frameworks with
monovalent ions combine lithium mobility with high computed electrochemical
stability |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8569803/ https://www.ncbi.nlm.nih.gov/pubmed/34677973 http://dx.doi.org/10.1021/jacs.1c07874 |
work_keys_str_mv | AT hanguopeng extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT vasylenkoandrij extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT nealealexr extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT duffbenjaminb extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT chenruiyong extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT dyermatthews extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT dangyun extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT danielslukem extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT zanellamarco extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT robertsoncraigm extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT kershawcooklaurencej extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT hansenannalena extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT knappmichael extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT hardwicklaurencej extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT blancfrederic extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT claridgejohnb extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability AT rosseinskymatthewj extendedcondensedultraphosphateframeworkswithmonovalentionscombinelithiummobilitywithhighcomputedelectrochemicalstability |